Cooling gaseous suspensions of titanium dioxide in the preparation of titanium dioxide pigments from titanium tetrachloride



Patented May 16, 1950 COOLING GASEOUS SUSPENSIONS OF TI- TANIUM DIOXIDE IN THE PREPARATION OF TITANIUM DIOXIDE PIGMENTS FROM TITANIUM TETRACHLORIDE James E. Booge, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware NoDrawing. Application July 23, 1947, Serial No. 763,176

11 Claims. (Cl. 23-202) 1 This invention relates to vapor phase processes for the manufacture of titanium dioxide pigments from titanium halides, and more particularly to a method for cooling the products of such a. process.

The vapor phase process for preparing such pigments generally comprises, in brief, the attack of a titaniferous ore with a gaseous halogen at elevated temperatures in the presence of a reducing agent, recovery and purification of the resulting titanium halide vapors, and reaction of the said vapors with an oxygen-containing gas in a suitable reaction chamber at high temperatures. The products of this vapor phase oxidation step issue from the reaction vessel in the form of a finely-divided solid titanium oxide, suspended in large volumes of hot, corrosive halogen-containing gases. The rapidity with which this gaseous suspension is cooled to below a reactive temperature determines to a great extent the precision with which the reaction can be controlled. At reactive temperatures the solid particles of titanium oxide will continue to grow rapidly in size as additional material forms and deposits on them, or as individual particles coalescef Consequently, rapid quenching of the reaction'to a relatively inactive temperature range is a prime requisite where the solid product is desired in a finely divided state. For greatest economy, processes for the oxidation of titanium halides are generally cyclic, with the by-product halogen being recycled to halogenate more of the titanium-bearing ore, producing additional quantities of the desired titanium halide for oxidation. It is important that the gases issuing from the oxidation chamber be maintained in as concentrated a state as possible, to permit their use for halogenation without expensive pretreatment to remove undesirable diluents. Therefore, quenching with cold air, the method ordinarily used for cooling finely divided solids, is impractical in the present application.

Quenching is achieved commercially by several means, with varying degrees of success. One method makes use of heat-exchange tubes, a relatively cool fluid being passed through the tubes, and the hot gases being circulated around them. The material of construction of such tubes presents a major problem where the gases are corrosive, as in the case of these halogen-containing products. The use of this type of indirect cooling apparatus is particularly unsatisfactory for cooling gaseous suspensions of solids. When the hot material'comes in contact with the heat z ,1 ticles are deposited on the cold surfaces, grad ually building up thereon as a thick coating. Ii, as in the case of pigment titanium dioxide, the solid is a non-conductor, the end result isthat the tubes quickly become insulated, heat trans-j for is greatly reduced, and the overall efliciency' is rendered very poor.

Separation of the solid oxide and hot product gases prior to cooling would make the cooling step easier, but, even if the separation could be" accomplished quickly enough to permit quench: ing before particle growth was excessive, the cor rosive nature of the gases makes the design of such a separating apparatus extremely diificult. Furthermore, it is characteristic of titanium dioxide that it is slightly plastic at elevated tem-Q peratures, with the result that its tendency to form a coating on the surfaces with which it comes in contact is accentuated. In a cyclonetype separator, for example, material depositing on the walls interferes with effective operation, and soon plugs the apparatus completely unlesscomplex scraping devices are employed.

It is accordingly an object of this invention to overcome the above and other disadvantages'of prior art processes. A particular object is to cool hot corrosive gaseous suspensions of finely di-' vided titanium dioxide. Another object is to minimize particle growth of such titanium oxide during the quenching operation. Yet another object is to effect the cooling under conditions allowing optimum heat transfer eificiency. A further object is to minimize buildup of titanium oxide on the surfaces of the conduits of the chamber during the cooling operation. An add-itional object is to quench hot gaseous materials; without substantially diluting the same with ob- J'ectionable foreign substances. Still another object is to cool large volumes of gases in equip: ment that is of relatively simple construction. A specific object is to effect cooling of suspensions of titanium dioxide in hot halogen-containing gases. -z-

The above and other objects are realized by the following invention which broadly comprises cooling a suspension of titanium oxide in hot, halogen-containing gases by contacting it with a further quantity of the same gases, cooled and recycled. Heat transfer is effected betweenthe hot materialsand the relatively cold gases, where-j by the former are rapidly cooled.

The invention may be more specifically described by reference to a preferred embodiment. A well known process for the preparation of ti-" exchange surfaces and is cooled, the solid par- 56 tanium oxide pigments involves the chlorination of titanium ore and the subsequent oxidation in the vapor phase, by oxygen, air, or other oxygen-containing gases, of the resulting titanium chlorides, in accordance, for instance, with the co-pending application of Holger H. Schaumann, Serial Number 653,428, filed March 9, 1946, now Patent No. 2,488,439. The oxidation reaction itself is exothermic, and high temperatures usually obtain therein, generally in the range of 900 to 1350 C. The titanium oxide product recovered suspended in a gas mixture, which latter comprises liberated chlorine,,perhaps excess oxygen, nitrogen, and the like. The suspension is of course at a very high temperature and must be cooled drastically and rapidly in'order toprevent excessive growth of the Tim particles and to allow the easy separation of thesolid mate-- rial.

corrosive nature of the chlorine-containing gases, this cooling in a rapid manner is-ncr-mally a difflcult and costly step. According to the present v process, however, the hotTiOz suspensionis simply contacted with afurther quantity. of the sam -mixture oilsases which haspreyiously been substantially freed from suspended titaniu-inzoxideparticles and cooled to a comparatively low tempfirature. Ehe latter cooling step is easily performed in a heat-exchanger-of-the usual type, Since. the absence of suspended solids permits efficient heat transfer throughs-urfaces, and the rapidity of cooling minimizes corrosion oi the equipment. No special apparatus is required for cooling; the gaseous suspension by this process, since-the normal passage of the gases through a Simple; conduit produces sufiicient mixing to effect the desired heat exchange. Theadded gases are: heated by the hot material and absorbiheat fromit, so that the-product of this operation is 'liiOasuspended inearelatively-cooler gas mixture of, larger volume-but of thesame composition as before. The solid T102 particles are later easily rfimcvedt-herefromby the action of cyclones, precipitators, filters, and other commonly used devices. The-gas mixture remainingcan then be divided, part .ofit. being recycled through the cooler and used'for further quenching, and part beingcirculated for-use-in the chlorination of ore, as-in'the usual cyclic process.

The following example is given-simply as: an illustration; of a preferred method of-carrying out thisfiinvention, and the invention is not to be limitcdfby the details setiorth.

Example T1014 vapor-and air were each separately preheated to 900 C. and injected into a reaction vessel constructed of fused silica. The proportions of air and TiCli weresuch as to give excess Ozjand the air contained 1% by volume of'water'vaporas a seeding agent. The reaction chamber Was heated initially to 1050 C. Upon admixture of the TiCl4 vapor and the air, a reaction occurred whereby the TiCLi was oxidized to T102 with the liberation of additional heat. The reactants were retained in the chamber for .2*second. The products exiting from the oxidation-vessel were at atemperature of l100 C., andcompr'ised solid T102 suspended in a gaseous mixture-having the composition: 31% byvolume of" chlorine, 67% by volume of nitrogen, and 2% by volume of oxygen. This hot suspension was passed through a silica conduit, leading from the reactor to a cyclone separator, at the rate of approximately 900 cubic feet per minute of gases, containing 6.1 pounds per minute of Ti02. 1015 Because of the high temperatures and the:

cubic feet per minute of recycled product gases at 50 0., having the composition given above, but cooled and free from T102, were admixed with the suspension as it passed through the conduit. The resulting mixture of gases and pigment had a temperatureof 300 C.

Two cyclones in series then removed most of the pigment from the gas stream, and the remainder was taken out by a, Cottrell precipitator'. The TiOz was then separately collected and foundto comprise fine particles having an average radius of .2 micron. Meanwhile, the gas stream, now-of course occupying a lesser volume, was divided into two parts. 210 cubic feet per minute; of gas were sent to chlorination apparatus to attack additional quantities of titaniferous ore and produce more T1014 vapors, and vi015 cubic feet per minute were cooled to 50 C. by passage through a conventional tubular heatexchanger, using river water as the cooling fluid,

and then recycled to cool further amounts of the T102 suspension issuing irom the oxidation reactionivessel.

The q-uanti-tyof gas to be recycled will of course be determined by the degree of cooling desired; the amount of material to be coo1ed,.and other similar factors. .Any amount, however small, willefiect some quenching. In general, it will be necessary to cool the gaseous suspension at least below 800 (3., and preferably below 600 C., to permit the use of metal equipment for separating the solids fromv the. gases, and to minimize particle growth.

The method of separating the solid particles from the, gasesis not critical, but it will generally be desirable to use a method which removes substantially all of the solid particles, to avoid fouling the surfaces of the cooler. It is prob ably most economical to remove the bulk of the solids in settling chambers, bafile chambers, cy

clones or other'simila-r devices, and to accomplish the final cleaning with electrical precipitation, as suggested above. Filters can also be used conveniently, but because of the corrosive nature'of the gases some inert filter medium, such asglass-or asbestos fiber or the new fabric disclosed in U. S. Patent 2,404,714, will be required.

The process as described above and shown in the example, provides a means for preparing pigmentary titanium dioxide from titanium tetrachloride by'vapor phase oxidation with satisfactory control of particle size. Control of particle size is essential to the development of optimum pigment properties, and elaborate: precautions have generally heretofore been neces= sary to efiect such control and to avoid growth of the particles beyond their optimum size (which is of the order of about .2 micron radius). It is necessary in such vapor phase production of TiOz to carry out the oxidation at very high temperatures in order initially to obtain proper particle dimensions and the desired crystal structure. However, these same high temperatures, if continued appreciably beyond the actual reaction stage, subsequently promote further and undesirable growth of the particles first formed. Itis believed that gaseous chlorine acts to remove titania from the smaller particles and to deposit it on the larger particles under such high temperature conditions. Accordingly, one problem is to form particles of proper dimensions and then immediately to lower thetemperature below the point at which growth will continue. Another important consideration is that gaseous halogens at elevated temperatures are extremely corrosive, so thatordinary metal equipment cannot generally be used until the product gases are complicated in design, this problem has not been easy to solve. My process now solves both of these problems in a very satisfactory and simple manner. It involves merely blending the oxidation reaction chamber eflluent gases with gases of the same composition previously cooled and recycled. The hot gases containing TiOz in suspension become cooled, by admixture with the cooler ha1ogenc0ntaining gases, so rapidly that it is possible finally to recover pigment titanium dioxide of the desired particle size. Furthermore, this blending can be effected in equipment which, as compared to that of the prior art, is of the utmost simplicity.

The many advantages of this novel process are apparent, Besides those noted above, a means is hereby provided for effecting cooling of hot suspensions of solids in halogen-containing gases by a rapid and efficient heat-exchange technique, no objectionable dilution of the said gases by foreign substances occurs, and the deleterious effects of corrosion by the gases and of build-up of the solids on the surfaces of the quenching system are minimized.

I claim:

1. A method for cooling a suspension of titanium oxide in hot halogen-containing gases which comprises admixing said suspension outside of the reaction zone wherein it is produced, with an additional quantity of the halogencontaining gases which have previously been cooled and freed of their titanium oxide burden.

2. A cyclic method for cooling a suspension of titanium oxide in hot halogen-containing gases which comprises contacting said suspension outside of the reaction zone wherein it is produced, with an additional quantity of the halogen-containing gases which have previously been cooled and from which the titanium oxide burden has been removed, effecting heat transfer by the said contact, thereafter separating out the cooled titanium oxide, and returning at least part of the cooled halogen-containing gases for reuse in contacting further quantities of the hot suspension.

3. A process for the preparation of titanium oxide which comprises oxidizing a titanium halide vapor with an oxygen-containing gas within a reaction zone, mixing the product suspension of titanium oxide in hot halogen-containing gases upon discharge from said zone with additional halogen-containing gases which have previously been cooled and freed of their titanium oxide burden, and recovering the resulting cooled titanium oxide from the gaseous medium.

4. A method for cooling a suspension of titanium oxide in hot chlorine-containing gases which comprises admixing said suspension upon discharge from the reaction zone wherein it is formed, with an additional quantity of the chlorine-containing gases which have previously been cooled and freed of their titanium oxide burden.

5. A cyclic process for the preparation of titanium oxide which comprises attacking a titaniferous ore with chlorine, oxidizing the resulting titanium chloride vapors with an oxygencontaining gas within a reaction zone, mixing the product suspension of. titanium oxide in hot chlorine-containing gases upon its discharge from said zone with additional chlorine-containing gases which have previously been cooled and freed of their titanium oxide burden, recovering the resulting cooled titanium oxide from the chlorine mixture, returning a part of the said chlorine mixture to attack additional titaniferous ore, and further cooling and recycling a part of the'said mixture to effect cooling of additional quantities of the hot titanium oxide suspension.

6. A process for the control of particle size of titanium oxide pigment prepared by the oxidation of titanium tetrachloride which comprises rapidly quenching the oxidation products by mixing therewith recycled chlorine-containing gas which has been cooled to below C. and from which titanium oxide has been separated.

'7. A process for the preparation of titanium oxide which comprises oxidizing titanium chloride vapor with an oxygen-containing gas at a temperature between about 900 and 1350 C., intimately contacting the product suspension of titanium oxide in hot chlorine-containing gases with additional chlorine-containing gases which have previously been cooled and freed of their titanium oxide burden, cooling the said suspension to below 600 C. in less than one minute by means of the said contact, and recoverin the cooled titanium oxide from the gaseous medium.

8. In a process for cooling a suspension of titanium oxide in hot halogen-containing gases subsequent to its discharge from a reaction zone by admixture with cool gases, the method of preventing dilution of the said halogen-containing gases which comprises separating titanium oxide from an initial quantity of the said suspension, cooling the halogen-containing gases thereafter remaining, and employing the thus-cooled gases as the medium for cooling further quantities of the said titanium oxide suspension being discharged from a reaction zone.

9. A process for controlling through rapid cooling the particle size growth of a TiOz pigment resulting from the vapor phase oxidation of titanium tetrachloride at temperatures ranging from 900-1350 0. within a reaction zone, which comprises directly mixing with the hot suspension of 'IiO2 in chlorine-containing gases upon its discharge from said zone, sufficient chlorine-containing gases previously recovered from the process, freed of TiOa and cooled to about 50 C1, to reduce the temperature of said suspension to below 800 C. within one minute from the oxidation reaction.

10. A process for controlling through rapid cooling the particle size growth of a TiOz pigment bein discharged in suspension in chlorine-containing gases from a reaction zone wherein the vapor phase oxidation at temperatures ranging from 900-1350 C. of titanium tetrachloride with air containing a small amount of water vapor takes place, which comprises recycling for direct mixing with said TiOz suspension sufficient chlorine-containing gases from the system previously freed of 'I'iO'e and cooled to about 50 0., to reduce the temperature of said suspension to below 600 C. within one minute from the time of occurrence of said oxidation reaction within said zone.

11. A process for controlling through rapid cooling the particle size growth of a T102 pigment obtained in the vapor phase oxidation, at temperatures ranging from 900-4350 C., of titanium tetrachloride with air containing a small amount Qmwaserapor, which smpmbas xairepkuy vmixin REFERENCES cmzn with hm wspgmmn of 9 'The following references aireof record :in Laininggasesdbamgndischarged-irom themactmn v this patent:

mnmufiiciem r lgyclad finlorin rcontaining g s s nm ucadm .nhe-fi t m and previ u ly freed or 5 UNITED STATES PATENTS I108 gmdwpaled o abuut 50 to reduce the Number Name Data:

temper -tune of fiaidvsuspensionto about 300 0. 2,340,610 Muskat-et a1. Fgb. 1,1944 ndwithin 19 .seconds from fiche Lime 0: the oxidaizion ,neaation mithinsaidzone.

JAMES LBOOKGE. 1o 

1. A METHOD FOR COOLING A SUSPENSION OF TITANIUM OXIDE IN HOT HALOGEN-CONTAINING GASES WHICH COMPRISES ADMIXING SAID SUSPENSION OUTSIDE OF THE REACTION ZONE WHEREIN IT IS PRODUCED, WITH AN ADDITIONAL QUANTITY OF THE HALOGENCONTAINING GASES WHICH HAVE PREVIOUSLY BEEN COOLED AND FREED OF THEIR TITANIUM OXIDE BURDEN. 